4481 4485.output

* GB784888 (A)

Description: GB784888 (A) ? 1957-10-16

Improvements in or relating to apparatus for the catalytic cracking ofhydrocarbon oils

Description of GB784888 (A)

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DE962631 (C) FR1126359 (A) NL92103 (C) US2798795 (A) DE962631 (C) FR1126359 (A) NL92103 (C) US2798795 (A) less Translate this text into Tooltip

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PATENT SPECIFICATION 7849888 Date of Application and filing Complete Specification June 22, 1955. No 18107/55. a x e S Application made in United States of America on June 24, 1954. Complete Specification Published Oct 16, 1957. Index at Acceptance: -Classes 1 ( 1), A 3 (A 1 A: B 2 A); and 32, El. International Classification: -B Olj Cl Og. COMPLETE SPECIFICATION Improvements in or relating to Apparatus for the Catalytic Cracking of Hydrocarbon Oils We, N V DE BATAAFSCHE PETROLEUM MAATSC Fi APPIJ, a company organised under the laws of The Netherlands, of 30 Carel van Bylandtlaan, The Hague, The Netherlands, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly

described in and by the following statement: - This invention relates to a new and improved apparatus for the catalytic cracking of hydrocarbon oils using a fluidised catalyst, the apparatus having both a novel flow arrangement and a novel arrangement of its essential component parts which is adapted to a specific type of catalytic cracking process allowing substantially increased optimum-conversion levels, substantially increased gasoline yields and product values, and substantially decreased coke production. In the specification of our Patent Application No 16616/55 (Serial No 784,546) there is described a process for the catalytic cracking of hydrocarbon oils, called " controlled catalytic cracking ", which affords substantially increased optimum conversion levels, substantially increased gasoline yields and product-values, and substantially reduced coke production This type of cracking operation cannot be carried out in the conventional catalytic cracking apparatus A catalytic cracking apparatus according to the present invention, allows such a process to be carried out both practically and economically with a low capital expenditure and low operating cost. According to the present invention there is provided apparatus for the catalytic cracking of hydrocarbon oils comprising in combination a fluidized catalyst regenerator vessel, a catalyst separator-hopper vessel, a catalyst stripper vessel, and a fluidized catalyst reactor vessel, each disposed substantially vertically and the four being arranged in plan roughly in a circle, the catalyst separator-hopper vessel being at the highest elevation and being provided with a standpipe opening into the fluidized catalyst reactor vessel near the lPice 3 s 6 d l bottom thereof, the fluidized catalyst reactor vessel being situated at a lower level and being provided with an inclined standpipe communicating with a substantially vertical riser line opening into the stripper vessel above the normal catalyst bed level therein, the stripper vessel being provided with an inclined standpipe communicating with a substantially vertical riser line opening into the regenerator vessel above the normal catalyst bed level therein, and the regenerator vessel being provided with an inclined standpipe communicating with a substantially vertical riser line opening into the catalyst separator-hopper vessel. In apparatus for use in a catalytic cracking process such as that described in the specification of Patent Application No 16616/55 (Serial No 781,916) the said riser line opening into the catalyst separator-hopper vessel is a riser reactor into which the oil vapour to be subjected to first stage catalytic cracking is injected at the bottom, the oil vapour injected into said reactor vessel being that to be subjected to second stage catalytic cracking.

In a modification of apparatus according to the present invention, the separator-hopper vessel is arranged wholly or partly within the upper part of the reactor vessel, and the fluidised catalyst regenerator vessel, the catalyst stripper vessel and the fluidised catalyst reactor vessel are arranged roughly in a circle. An apparatus according to the present invention will now be described with reference to the accompanying drawing, in which Figure I shows the arrangement of the main vessels and lines of the plant in oblique projection, and Figure II shows a plan of the arrangement. Referring to Figure II, the apparatus is arranged so that the catalyst circulates (counter-clockwise as the apparatus is shown in Figure II) through four vessels which are arranged in plan roughly in a circle In circulating, the catalyst undergoes a number of changes in elevation In each case the raising of the catalyst to a higher elevation is effected in a confined vertical conduit, the catalyst being 784,888 transported in the form of a dilute suspension and horizontal movement around the circuit shown in the plan view is, in each case, effected by movement of the catalyst by gravity in an inclined confined path in the form of a dense (pseudo-liquid) phase. Referring now also to Figure I, the apparatus comprises a substantially vertical riser reactor 11, forming a first stage catalytic cracking reactor and four vertically disposed essentially cylindrical vessels which are a fluid catalyst regenerator vessel 1, a catalyst separator-hopper vessel 2, a second stage fluid catalyst reactor vessel 3 and a fluid catalyst stripper vessel 4 The separator-hopper vessel 2 is the most elevated of the vessels, being approximately level with the top of the regenerator vessel. The reactor vessel 3 is at a lower position and the stripper vessel 4 is preferably located at a still lower elevation Each of these vessels 1-4 is provided, preferably substantially at the bottom, with an inclined standpipe 5 6, 7, or 8 respectively, which standpipes 5-8 are straight and preferably inclined to the vertical at an acute angle lying in the range from about 200 to about 450. Starting at the elevated separator-hopper vessel 2, the catalyst descends under gravity as a dense (pseudo-liquid) stream through the standpipe 6 which opens into the bottom of the reactor vessel 3, into which the oil fraction to be subjected to second stage cracking is introduced at A, the catalyst thereby traversing one section of the horizontal path of travel. From the reactor 3 the catalyst again descends under gravity as a dense (pseudo-liquid) stream, this time through the standpipe 7 to a position which in plan is directly under the stripper vessel 4, thereby traversing a second leg of the horizontal path of travel It is then raised into the stripper vessel 4 through a vertical line 9, for

example by means of steam introduced at B The catalyst then flows under gravity and as a dense phase through the standpipe 8 to a position which in plan is under the regenerator vessel 1, thereby traversing a third leg of the horizontal path of travel. After being raised into the regenerator vessel 1 through the vertical line 10 by means of air and/or steam introduced at C, the catalyst again flows under gravity as a dense phase through the standpipe 5 to a point from which it is raised to the separator-hopper vessel 2 through the first stage catalytic cracking reactor 11 by means of the vaporised oil feed which is to be subjected to first stage cracking in the reactor 11 and is introduced at D The reactor 11 is vertical except for the bend at its top which is necessary to enable the catalyst to enter the separator-hopper vessel 2 tangentially Thus, the catalyst flows under gravity and as a dense phase through the standpipes 5-8 to complete the horizontal displacement of the circulation path and at intermediate points is raised through the vertical lines 9 and and the reactor 11. The lines 9 and 10 extend up into the stripper vessel 4 and regenerator vesel 1 respectively, to a height above the normal levels of 70 the fluidized catalyst beds in them, as indicated at levels X and Y respectively, and, therefore, they open into the upper, or disengaging, space of these vessels 1 and 4 These lines 9 and 10 and also the reactor 11, which are 75 constructed to be as straight as possible and substantially vertical, are of such diameter that at the flow rate for which the plant is designed the linear velocity therein is well above the critical velocity, the latter being the superficial 80 velocity above which a so-called dense or pseudo-liquid catalyst phase cannot separate. The standpipes 5, 6, 7 and 8 operate with the catalyst always flowing under gravity as a dense or pseudo-liquid phase 85 In order to obtain a Proper pressure balance, so that the circulation of the catalyst may be effected, it is necessary that the standpipe 6 should open into the reactor vessel 3 near the bottom substantially as shown in Fix I Flow 90 control valves 12 and 13 are provided only on the standpipes 5 and 8 respectively through which the catalyst flows from the regenerator 1 and the stripper 4 The other standpipes 6 and 7 require no such valve A back-pressure 95 control valve 14 is provided in the vapour effluent line 15 which leads from the stripper vessel 4 and opens into the reactor vessel 3 near the top At the top of both the separatorhopper vessel 2 and the reactor vessel 3 there 100 is provided an outlet-pipe 16 or 17 respectively, through which the vapour effluents flow to separate fractionating columns In these fractionating columns separation is effected into a gas-gasoline overhead fraction and a bot 105 tom fraction which, from one or both columns, serves as the feed

for the second stage reactor 3 into which it is introduced at A Regeneration gases issuing from the regenerator vessel 1 are led through a line 18 to the flue 110 Only the important lines and features of the anparatus are shown in the drawing Actually, all four of the vessels 1-4 are provided near the top with cyclone separators of conventional design having depending dip-legs Also, there 115 are vapour distributors, e g perforated pipe distributors, at the bottom of the cylindrical parts of the regenerator vessel 1 and the stripper vessel 4 for the distribution of air, introduced at E, and stripping steam, es' 120 For the sake of clarity and simplicity these and other conventional features are not shown in the drawving It is to be understood however that these feautres, as well as various minor valves, aeration lines, control instruments, 125 and the like auxiliary equipment will normally be included in the apparatus. The arrangement of all the four vessels 1-4 in plan roughly in a circle as shown is the preferred arrangement, but in a modifica 130 784,888 tion of apparatus according to the present invention it is possible to construct the separator-hopper vessel 2 wholly or partly within the upper part of the reactor vessel 3 the three vessels 1, 3 and 4 then being arranged roughly in a circle with the separator-hopper vessel 2 within the vessel 3 directly above the reaction zone In this arrangement it is essential, as in the case described, that there be no communication between the two vessels, except through the catalyst line 6 opening into the reactor vessel 3 near the bottom. The apparatus described with reference to the drawing is applicable and may be used with advantage for the controlled catalytic cracking of hydrocarbon oils by the process described in the aforesaid co-pending application, to which reference should be made for details as to the process conditions It will be appreciated however that other catalytic cracking processes may be carried out in apparatus according to the present invention Whilst it is particularly suitable for a two-stage process, it may also be used for a single stage process, the vapour introduced at D then being steam or the like, and the oil feed being introduced into the reactor 3 at A.

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* GB784889 (A)

Description: GB784889 (A) ? 1957-10-16

Improvements in or relating to energy regulating services



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PATENT SPECIFICATION 784,889 / g Date of Application and filing Complete Specification Aug 4, 1955. No 22477/55. Application maidne in France on Sept 17,1954. Complete Specification Publised Oct 16, 1957. Index at Acceptance:-Class 38 ( 5), Bl S( 1 B 10), B 2 C( 6 C 2: 8 A). International Classification:-Ho 2 c. COMPLETE SPECIFICATION Improvements in or relating to energy regulating services We, SCINTEX, a Body Corporate duly organized according to the French laws, of 42 to 50, rue de l'Industrie, Courbevoie, (Seine), France, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The invention relates to a device for regulating energy supplied to an electric load. Some electric generators, as for instance the magnetic flywheels used

on vehicles of the motor-cycle type give a voltage which varies according to the speed of rotation of the flywheel and also according to the number of loads placed in operation At high speeds and if a single load of low power rating is placed in service, the voltage may become excessive and cause damage to or even the destruction of this load. The object of the present invention is to obviate this drawback by regulating the energy supplied to the load at a critical level. The invention consists in a device for regulating energy supplied to an electric load, comprising a source of current, a fixed contact connected to this source, a resiliently mounted metallic blade in series with the load, a movable contact carried at one extremity of this blade, a conducting resistance wire connected to a fixed point and to the said extremity of the blade so as to urge the movable contact against the fixed contact, the resistance wire being in parallel with the blade and the load, so that when the voltage of the source exceeds a critical voltage the resistance wire expands and cuts off the supply of the load, such interruptions being short but more and more frequent as the voltage rises, whereby the mean value of the energy supplied to the load is regulated. The features of the invention will appear in a more precise manner from the description which will be given hereinafter with lPrice 3 s 6 d l reference to the drawing which shows in diagrammatic form a device embodying the invention. In the drawing, a rigid blade 1 is mounted on a flat spring 2 secured to a terminal 3 50 which is connected to one end of a load, the other end thereof being earthed The blade 1 carries a contact 4 at its free end A conducting resistance wire 5 is stretched between the contact 4 and a fixed point 6 The 55 contact 4 is placed opposite another contact 8 carried by an elastic blade 9 supported at The lower end of wire 5 is earthed with or without an interposition of an adjusting resistance 7 and the contact 4 is pulled to 60 ward the contact 8 against the action of the flat spring 2 by the tension of the wire 5 A cut-off switch 11 controls the supply of current from the positive pole of a source having the negative pole earthed and a screw 12 65 makes it possible to adjust the location of the contact 8 If the applied voltage is lower than a critical voltage, the current passes through 10, 9, 8, 4, 1, 2 and 3 into the load in a continuous manner, the slight heating of 70 the wire 5 being made up by the heat losses to the surrounding medium. When the voltage increases to above the critical voltage, the wire 5 expands and, allows the blade to move under the action 75 of the flat spring 2 to open the circuit. The wire 5, to which power is now no longer supplied, cools down, the

contacts 4 and 8 engage each other and the cycle is repeated The current is thus interrupted, 80 at a frequency which increases with the voltage. By operation of the screw 12 and possibly by alteration of the resistance 7, it is possible to adjust the system at will and in particular 85 to adapt it according to the ambient temperature, variations of which affect the cooling time for the wire 5 and consequently the duration of the current interruption.


* GB784890 (A)

Description: GB784890 (A) ? 1957-10-16

Improvements in or relating to fuel elements for nuclear reactors



BE550544 (A) DE1029495 (B) ES230518 (A1) FR1156074 (A) BE550544 (A) DE1029495 (B) ES230518 (A1) FR1156074 (A) less Translate this text into Tooltip



PATENT SPECIFICATION fnventor: KENNETH HENRY DENT Date of filing Complete Specification Aug 16, 1956. Application Date Aug 25, 1955. Complete Specification Published Oct 16, 1957. 784890 No 24513/55. Index at Acceptance: -Class 39 ( 4), P 3 C. International Classification: -G 21. COMPLETE SPECIFICATION Improvements in or relating to Fuel Elements for Nuclear Reactors We, UNITED KINGDOM ATOMIC ENERGY AUTHORITY, London, a British Authority, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be perfomed, to be particularly described in and by the following statement: - This invention relates to fuel elements for nuclear reactors and the invention is concerned with a form of fuel element suitable for use as one of a column of similar elements in a vertically orientated nuclear reactor, that is, a nuclear reactor comprising a moderator structure having vertical fuel element channels. The operating temperature of a nuclear reactor designed as a part of a steam/electricity generating plant should be as high as possible for the efficient production of electricity and accordingly it can be said that the factors in the reactor design limiting its maximum safe operating temperature also limit the efficiency of electricity generation At the present time the (principal of these factors is the creep strength of the material used to enclose the nuclear fuel (the material commonly referred to as the canning material) and any design which may be directed to the removal of loads, and hence creep deformities, from the canning material has merit, especially in view of the fact that the elements will be expected to reside in the reactor for a long time to achieve a high degree of burn up ( 3000 megawatt days per tonne) In one proposal to this end it has been suggested that, in a vertically orientated reactor, the fuel elements should be individually supported so that the stresses should never exceed those due to a single element In yet another proposal it has been suggested that the stressed parts of the canning material should be preferentially cooled. According to the present invention a fuel element for use in a vertically orientated nuclear reactor comprises a nuclear fuel member enclosed by a protective sheath of canning material and an end supporting means for the lPrice 3 s W 1 e 4 6 O _ - <; fuel element comprising a load carrying member having a creep strength superior to that of the protective sheath material penetrating and sealed to the protective sheath, and adapted to be fixed to the nuclear fuel member

so that 50 stresses due to the weight of the nuclear fuel member are carried directly by the load-carrying member. The load carrying member may be at either end of the fuel element to provide either for 55 a suspended element which is in tension and thus free from bowing or a supported element which behaves as a strut in compression and is liable to bowing but is more easily dischargeable from the reactor The elements 60 may be individually supported, or supported one upon or from the other in strings by providing load carrying members at both ends of the fuel elements which can be associated with one another in adjacent elements to take the 65 compression or tension in the strings. The load carrying member is preferably made of a material having a low neutron absorption (e g beryllium or zirconium alloy) as there will be many of these members inside 70 a charged reactor core Other considerations may however prevent the use of low neutron absorbing materials and it then becomes important that the volume of the load carrying member should be as small as possible A 75 screwed pin having one end screwed into the nuclear fuel member and the other end available to connect with an external part to support the fuel element provides a simple low volume device 80 The arrangement of individually suspended fuel elements according to the invention is of particular interest as it offers not only satisfactory operating conditions without bowing tendencies, but also safer discharging from the 85 reactor as the discharging operation need not involve stressing the canning material. An individually supported fuel element according to the invention is now described with reference to the drawing accompanying 90 784,890 the provisional specification in which Fig 1 is a sectional elevation and Fig 2 is a plan view of Fig 1. In the drawings a fuel element comprises a vertical fuel member 10 enclosed by a sheath 11 made from a tube 12 having circumferential fins 13, a lower end cap 14, and an upper enid cap 15 An end supporting means in the form of a stainless steel stud 16 penetrates the end cap 15 part of the sheath 11 and is screwed into the fuel member 10 at a thread 17 The stud 16 is bonded to the cap 15 along the surface 18, so as to be sealed to the sheath in passage therethrough. The stud 16 has screwed to it a lifting and support member 19 which comprises a boss 20 with three fixed lifting legs 21 and three springloaded pivoted legs 22 The legs 22 pivot on pins 23 and the spring loading is provided by springs 24 in a sense to move the legs 22 outwards. Each leg 22 has a rising part 25 which offers a face 26 which can be depressed to move the legs 22 inwards against the spring loading (during charging and discharging of the fuel element) to the position

shown dotted. The fuel element is shown lodged in a graphite moderator structure 27 which isshaped to provide a coolant channel 28, a ledge 29 in which the legs 22 rest so as to support the fuel element, and a conical cut-away part 30. A heat insulating disc 31 of aluminium oxide is provided between the fuel member 10 and the end cap 14 to reduce heat transfer to the end cap 14. In the assembly of the fuel element the finned tube 12 is closed at its lower end by inserting the end cap 14 supporting the disc 31 and welding along the rim 32 The fuel member 10 is then inserted and the assembly of cap 15 with bonded stud 16 is screwed into place with a tool which enters holes 33 This brings flanges 34, 35 into contact, which are then sealed with an edge weld 36 The lifting and support member 19 is then attached. In the charging of the fuel element into the reactor the element is supported in a grab by the legs 21 and a plunger in the grab acting on faces 26 keeps the legs 22 to the inward positioni At a suitable point (the tolerance of which may be liberally taken) in the insertion of the element, the force of the plunger is withdrawn and the legs 22 move outwards under the loading of springs 24 to touch the 55 walls of the channels 28 and to follow the conical part 30 to reach the ledge 29 when the element becomes self-suspended. In discharging the fuel element a grab is lowered which has a sk irt of larger radius than 60 that of the legs 21 and is arranged to be located angularly by the legs 22 thereby to locate a lifting part of the grab under the legs 21.


* GB784891 (A)

Description: GB784891 (A) ? 1957-10-16

Novel unsaturated ketones and a process for the manufacture thereof



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COMPLETE SPECIFICATION Novel Unsaturated Ketones and a process for the Manufacture thereof We, F. HOFFMANN-LA ROCHE & CO., A1CTIENGESELLSCHAFT, a Swiss Company, of 124-184 Grenzacherstrasse, Basle, Switzer- land, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention is concerned with novel unsaturated ketones and with a process for the manufacture thereof. The unsaturated ketones provided by the invention are substances which may be represented by the general formula: <img class="EMIRef" id="026598905-00010001" /> in which R stands for a 6-alkyl-2,6-dimethylcyclohexen-(l)-yl or 6-alkyl-2,6 - dimethylcyclohexen-(2)-yl radical wherein the ailcyl group contains from 2 to 4 carbon atoms. These ketones possess new scent nuances and may be used in the preparation of odoriferous compositions and perfumes. According to the process provided by the present invention, the unsaturated ketones aforesaid are manufactured by treating a ketone having the general formula: <img class="EMIRef" id="026598905-00010002" /> wherein 1S1 represents an alkyl radical having from 2 to 4 carbon atons, with substantially water-free sulphuric acid below 0 C. or with phosphoric acid at ca. 20"--35"C. according to whether compounds

having a double bond in the 11,2l- or 21,31-poskions respectively are required. The ketones which may be used as starting materials include, for example, 6,10-dimethyldodecatrien-(3,5,9) - one - (2) and 6,10,12-trimethyl tridodecatrien- (3,5,9)-one-(2). The 6, 10-dirnethyl-dodecatrien-(3,5,9)-one-(2) may be obtained, for example, as follows: 600 g. of 3-methyl-penten-(1)-ol-(3) were cooled to + 15 C. with an ice bath, then 1,800 ml. of concentrated aqueous hydrochloric acid (37%) were poured into the reaction vessel. The mixture was stirred for 30 minutes. The oil, comprising essentially 1chloro-3-methyl-pentene-(2) was separated, washed three times with 500 ml. of water and dried over calcium chloride. 4 litres of benzene, 1,040 g. of ethyl aceto-acetate and 378 g. of sodium methylate were stirred into a 12 litre flask. 696 g. of 1-chloro-3-methyl-pentene-(2) were added from a separatory funnel in 2 hours at 60"C. The stirring was then continued at 60"C. for 16 hours. The mixture was diluted with 4 litres of water. The oil was separated and the benzene was distilled off under vacuum. The thick residue, 3-carbethoxy-6-methyl-octen-(5)-one-(2), was placed in a 5-litre flask with 2 litres of ethyl alcohol, 1 litre of water and 500 g. of potassium hydroxide. This was stirred for 2 hours, then allowed to stand for 16 hours, thereby forming the potassium salt of 3-carboxy-6-methylocten-(5)-one-(2). Concentrated hydrochloric acid was added to the stirred reaction mixture from a separating funnel until the mixture became strongly acid. The oil layer was removed, and the aqueous portion was extracted with 1 litre of benzene. The combined oils were water washed and fractionated to yield 6-methyl-octen-(5)-one-(2), distilling at 65" C./10 mm., nn25=1.4412. 84 g. of metallic sodium was dissolved in 3 litres of liquid ammonia. Acetylene was bubbled into the stirred solution until its colour changed from blue to a white. 420 g. of 6-methyl-octen (5)-one-(2) was dissolved in 500 ml. of diethyl ether and dropped into the stirred reaction mixture in 1 hour. Stirring was then con tinued for 3 hours while a slow stream of acetylene was bubbled in. The addition of acetylene was then stopped, but the stirring was continued for about 15 hours. The ammonia was then distilled off and the residue in the reaction vessel was washed with 2 litres of 5% aqueous sulphuric acid. The product was then water-washed, dried over anhydrous calcium sulphate and fractionated to yield 3,7-dimethyl-nonen-(6)-yn-(1)-ol-(3), distilling at 89Cj10 mm. n-5 1.4612. 300 g. of 3,7-dimethyl-nonen-(6)-yn-(1)-ol-(3), 30 g. of 5 % lead/palladium/calcium- carbonate catalyst [LINDLA1R, Helvetica Chimica Acta 1952, 35, 446] and 300 ml. of petroleum ether were placed

in a flask provided with a stirrer and hydrogenated at 25 c30 C. at one atmosphere hydrogen pressure until 1.9 mols. of hydrogen were consumed. Fractionation of the product gave 3,7-dimethyl-nonadiene-(1,6)-ol(3) distilling at 132 C./86 mm., nD25 = 4603. In a flask fined with a stirrer, thermometer, dropping funnel, and a cold water bath, were placed 1,500 ml. of water, 250 g. of sodium dichromate, 125 ml. of glacial acetic acid, 200 ml. of benzene, and 125 g. of 3,7-dini-ethyl- nonadien-(1,6)-ol-(3). To the stirred reaction mixture was added a solution of 125 ml. of concentrated sulphuric acid in 400 ml. of water over a period of 2 hours. During the addition, the temperature was controlled at 40 C. The stirring was continued for an additional hour; then 1 litre of water was added. The oil layer was removed with a separating funnel, and the aqueous layer was extracted with 400 ml. of benzene. The oil and benzene extracts were combined and washed until neutral. The oil was distilled through a column under vacuum. The product, 3,7-dimethyl-nonadien-(2,6)-al-(1), distilled at 135 -1370C./25 mm., nD25=1.4830. The semicarbazone derivative melted at 159"C. 45 g. of 3,7-dimethyl-nonadien-(2,6)-al-(1), 50 g. of aluminum isopropylate, 600 ml. of acetone and 600 ml. of benzene were placed in a 2-litre flask and stirred at reflux temperature for 24 hours. The cooled reaction mixture was washed first with dilute hydrochloric acid and finally with water until neutral. The benzene was distilled off, and the product was fractionated under high vacuum, the desired product 6,10dimethyl-dodecatrien-(3,5,9)-one-(2) being obtained in a fraction distilling at 102 103 C. /0.2 mm., nD23 =1.5223. The 2,4-dinitro- phenyl hydrazone derivative melted at 117 C. The other starting ketones may be obtained similarly: for example, by using 3,5-dimethyl- hexen-(1)-ol-(3) instead of 3-methyl-penten (1)-ol-(3). Depending on the acid agent used for effecting the cyclisation, there are obtained cyclic ketones having structures analogous to -ionone or of -ionone. Thus, as indicated hereinbefore, final ketones having structures analogous to that of ss-ionone are obtained if the ketones used as starting materials are treated with substantially water-free sulphuric acid at below 0 C. and final ketones having structures analogous to that of Sionone are obtained if the ketones used as starting materials are treated with syrupy phosphoric acid at ca 200-350C. When using sulphuric acid to effect the cyclisation it is advantageous to carry out the reaction in the presence of acetic acid as the formation of by products due to polymerisation is lessened thereby.

The following examples are illustrative of the present invention: EXAMPLE 1. A solution of 350 g. of concentrated sulphuric acid and 75 g. of glacial acetic acid was cooled to - 30 C. 100 g. of 6,10-dimethyl-dodeca.rien-(3,5,9)-one-(2) were added dropwise in 45 minutes, keeping the temperature at -20" to -30 C. The stiff reddish coloured mixture was warmed up to 0 C. and stirred for 10 minutes. This was then poured on to 1,500 g. of crushed ice. The product was extracted with toluene, washed with water, then with 20% aqueous sodium hydroxide solution, and finally with a saturated sodium chloride solution containing a few drops of acetic acid. On fractionation, 4-[6l-ethyl-2l,6l- dimethyl-cyclohexen-(1)-yl] - buten-(3)-one (2) was obtained in a fraction distilling at 86.50-870C./0.3 mm., nD25= 1.5165. This compound has an odour reminiscent of violets, but with cedar notes. The 2,4-dinitro-phenyl hydrazone derivative melted at 126"C. EXAMPLE 2. 51.4 g. of 6,10-dimethyl-dodecatrien-(3,5,9)one-(2) were added drop by drop to 3S6 g. of 85% aqueous phosphoric acid with vigorous stirring. The addition was made in 30 minutes while the temperature was kept at 30"--35"C. The reaction product was poured into 1,500 ml. of cold water. The product was extracted with benzene and the extract was subjected to steam distillation. The distillate was benzene extracted, and the extract was fractionated. 4-[61-ethyl - 21,6l - dimethyl-cyclohexen-(21) yl] buten-(3)-one-(2) was obtained as a fraction distilling at 73 C./0.10 mm., nD2= 1.497. The 2,4-dinitro-phenyl hydrazone derivative melted at 1600C. 4-[6l-ethyl-2l,6l- dimethyl-cyclohexen-(21)-yl] -buten-(3)-one-(2) has a pleasant fragrance reminiscent of that of orris root. EXAMPLE 3. 94.6 g. of refractionated 6,10,12-trimethyltridecatrien-(3,5,9)-one-(2), b.p. 10-+ C./0.1 mm., nD=1.515 were added to 580 ml. syrupy aqueous phosphoric acid (85% by weight phosphoric acid) during 30 minutes at a temperature maintained between 24 C. and 30 C. The stirring was continued 5 minutes longer at 30 C. The mixture was then poured into 2.2 litres of ice water. The upper layer was separated, and the aqueous layer was extracted novice, each time with 500 ml. of benzene. The benzene solution was water washed until neutral. The- crude reaction product was distilled with steam, the upper (organic) layer of the distillate was separated and the aqueous (lower) layer was extracted with 100 ml. of benzene. The organic layer and the benzene extract were combined and the benzene was removed under

reduced pressure. The residue was fractionated under high vacuum. The fraction distilling at 94"- 97"C./0.2 mm., nD25 = 1.4958= 1.4963 was 4[614sobutyl-21,6' - dimethyl - cyclohexen-(21)yl]-buten-(3)-one-(2). This product has a penetrating woody odour reminiscent of cedarwood and sandalwood and is useful as an odorant in the preparation of perfumes. ExAMPLE 4. A solution of 700 g. of concentrated sulphuric acid and 150 g. of glacial acetic acid was cooled to -30 C. Then 234 g. of refractionated 6,10,12 - trimethyl - tridecatrien (3,5,9)-one-(2), b.p. 104 C./0.1 mm., nD25= 1.515, was added during 45 minutes, the temperature being kept between - 30 C. and - 20 C. An efficient powerful stirrer was needed as the solution became very thick. The mixture was warmed up to 0 C. and stirred for 10 minutes at that temperature. It was then poured on to 3,000 g. of crushed ice and allowed to stand until the ice melted. The organic layer was separated, and the aqueous layer was extracted with toluene. The organic layer and the toluene extract were combined and washed with 500 ml. of water, 500 ml. of 20% aqueous sodium hydroxide solution and finally with 500 ml. of a saturated aqueous sodium chloride solution containing a little acetic acid. The oil was dried over anhydrous calcium sulphate, the solvent was removed and the residue was fractionated. The fraction distilling at 92"C./0.3 mm., nn25 = 1.505-1.507, comprised essentially 4[6i - isobutyl - 21,61 dimethyl-cyclohexen-(11)-yl] - buten - (3)-one (2). This compound has an odour similar to that of 4-[61-isobutyl-2l,6l-dimethyl-cyclohexen-(21)-yl] -buten-(3)-one-(2), but distinguishable from the odour of the latter in being not quite so woody and in having leafy accents. The compound is useful as an odorant in the preparation of scented compositions. What we claim is: - 1) Substances of the general formula: <img class="EMIRef" id="026598905-00030001" /> in which R stands for a 6-allcyl-2,6-dimethyl- cyclohexen-(l)-yl or 6-alkyl-2,6 - dimethylcyclohexen-(2)-yl radical wherein the alkyl group contains from 2 to 4 carbon atoms. 2) 4- [61-ethyl-21,61 - dimethyl - cyclohexen(ll)-yl] -buten-(3)-one-(2). 3) 4-[6l-ethyl-2l,6l- dimethyl- cyclohexen- (21)-yl] -buten-(3)-one-(2). 4) 4- [61-isobutyl-2l,6l-dimethyl-cyclohexen- (21)-yl] -buten-(3 )-one-(2). 5) 4- [614sobutyl-21,61-dimethyl-cyclohexen- (ll)-yl]

-buten-(3)-one-(2). 6) A process for the manufacture of those substances of the general formula given in claim 1 in which R stands for a 6-alkyl-2,6dimethyl-cyclohexen-( 1)-yl radical wherein the alkyl group contains from 2 to 4 carbon atoms, which process comprises treating a ketone of the general formula: <img class="EMIRef" id="026598905-00030002" /> wherein R1 represents an alkyl radical having from 2 to 4 carbon atoms, with substantially water-free sulphuric acid at below 0 C. 7) A process in accordance with claim 6, wherein the cyclisation is carried out in the presence of acetic acid. 8) A process for the manufacture of those substances of the general formula given in claim 1 in which R stands for a 6-alkyl-2,6dimethyl-cyclohexen-(2)-yl radical wherein the alkyl group contains from 2 to 4 carbon atoms, which process comprises treating a ketone of the general formula given in claim 6 herein with phosphoric acid at ca. 20"--35"C. 9) A process for the manufacture of the substances claimed in claim 1 hereof, substantially as described with reference to the examples given.

* GB784892 (A)

Description: GB784892 (A) ? 1957-10-16

Piperidine derivatives and process for their manufacture

Description of GB784892 (A) Translate this text into Tooltip



PATENT SPECIFICATION

784,892 Date of Application and filing Complete Specification: Sept 23, 1955. No 26449/55. Application made in Switzerland on Sept 28, 1954. Application made in Switzerland on May 3, 1955. Application made in Switzerland on Aug 24 1955. Complete Specification Published: Oct 16, 1957. Index at acceptance:-Class 2 ( 3), C 1 (A 10: B 2), C 1 F 2 (A 2 A 3: C 4: D 3), C 2 A( 3: 5: 9), C 2 B 3 (A 4: B: Gi: G 4), C 2 R 17. International Classification:-CO 7 d. COMPLETE SPECIFICATION Piperidine Derivatives and process for their Manufacture We, SAN Doz LTD, Basle, Switzerland, a Body Corporate organised according to the laws of Switzerland, do hereby declare the invention, for which we pray that a patent may be granted us, and the method by which it is to be performed, to be particularly described in and by the following statement: - The invention relates to new piperidine derivatives and salts thereof, a process for preparing them, and therapeutic compositions containing them. The invention provides piperidine derivatives having the formula ja e,,a tt 8 Ik RS I wherein R,, R 2, R 3 and R 4 are like or different and represent hydrogen, methyl, chlorine, bromine, or methoxy, and R, is hydrogen or an alkyl radical; and acid addition salts of such piperidine derivatives. The invention also provides a process for the preparation of a piperidine derivative or an acid addition salt thereof comprising reacting a secondary amine of the formula 43 KR II wherein R, R,, R 3 and R, are like or different and represent hydrogen, methyl, chlorine, bromine, or methoxy, with a substituted piperidine of the formula el N et c H-la ct I CH /Co-CI CJ-lx R 5 III wherein R, represents hydrogen or alkyl and X represents chlorine or bromine. In carrying out the process of the invention particularly useful compounds are obtained by choosing secondary amines as starting materials in which: R 1 and R 2 are both hydrogen atoms, and/or R, is hydrogen, and R, is chlorine, bromine, methyl or methoxy, or R, and R, are both chlorine or bromine, or R 2 and( R 4 are both hydrogen, or in which one or both substituents R 1 and R, are in the rm-position to the N-atom, and in which R 5 in the piperidine derivative is hydrogen or methyl or ethyl, with consequent formation of the corresponding compounds of the Formula I. The process may for example be carried out by dissolving a secondary

amine of Formula II in a solvent, such as for example benzene, toluene, or xylene, and reacting it with a halogenated piperidine derivative of Formula III at room temperature or at increased temperature, for example at the boiling temperature of the reaction mixture, with good stirring and the addition of a hydrogen halide-binding or halogen-binding condensation agent, for example an alkali metal hydroxide, alkali metal amide, alkali metal carbonate or copper powder After completion of the reaction, the reaction product is recovered by means of suitable working up of the reaction mixture and distillation in vacuum The further purification can be effected by conversion into a suitable salt and subsequent regeneratiorn of the free base, lPrice 3 s 6 d l 2 784,892 The hitherto unknown compounds prepared according to the present process are oily or crystalline at room temperature and form stable solid salts with acids They are active spasmolytically and should find use in therapeutics as spasmolytics Furthermore they serve as intermediates for the synthesis of therapeutically-active compounds Thus, for example, by treatment with elementary sulphur in the presence or in the absence of a catalyst, for example iodine, or by treatment with sulphur dihalides, they lead to phenothiazine derivatives with valuable therapeutic properties, as for example the raising to a higher power of the effect of narcotically, hypnotically and analgesically acting pharmaceutics These phenothiazine derivatives are therefore therapeutically suitable for use in preparation for narcosis; they can however also be used in the treatment of allergic illnesses, and as spasmolytics or as neuroplegics. The following Examples illustrate the invention without limiting it; temperatures are given in degrees Centigrade. EXAMPLE 1. N lin-chloro-phenyll-N-l 2-(piperidyl2 ')-ethyl-1 l-aniline. g N-(m-chloro-phenyl)-aniline (B p = /11 mm Hg), prepared according to F. Ullman, Ann 355, 338 ( 1907), are dissolved in 800 cc of absolute xylene, treated with 25 3 g of finely-powdered sodamide, and the mixture is held at the boiling point under reflux during 2 hours with stirring using a bath ternperature of 180 Then, without interrupting the heating, 104 5 g of 2-(piperidyl-2 ')-1chloro-ethane (B p 84 /12 mm Hg, Beilstein 4 Aufl 20, 105), dissolved in 100 cc of absolute xylene, is added dropwise within 2 hours and the mixture is heated with stirring during a further 2 hours It is then cooled and the excess sodamide destroyed by the addition of g of ammonium chloride After addition of 200 cc of xylene the reaction solution is extracted 3 times, each time with 300 cc of water The xylene layer is then extracted, once with 400 cc, and then 3 times with 100 cc of dilute

acetic acid The acetic acid extract is made alkaline to phenolphthalein with 200 cc. of concentrated caustic soda solution, and extracted with a total of 400 cc of benzene The benzene solution, dried over potash and filtered, is concentrated as far as possible under partial vacuum at a bath temperature of 80 . The residue is first freed from excess 2(piperidyl-21)-l-chloro-ethane at 14 mm Hg. and using a bath temperature of about 150 , and then distilled under high vacuum The main fraction which passes over between 165 and 190 , under 0 01 mm Hg, is collected. The analytically pure N-lrn-chloro-phenyllN l 2-(piperidyl-21)-ethyl-ll-aniline boils under O 01 mm Hg at 170 -175 . For preparation of the hydrochloride 9 07 g of the base is dissolved in 35 cc of absolute ethanol and the solution is made acid to Congo with ethanolic hydrogen chloride, whereupon the hydrochloride separates out The analytically pure N lmn-chloro-phenyll -N l 2-piperidyl-2 ')-ethyl-ll -aniline-hydrochloride melts at -177 . EXAMPLE 2. N lm-chloro-phenyll -N l 2-(N'-ethylpiperidyl-21)-ethyl-1 l -aniline. 52.8 g N-(m-chloro-phenyl)-aniline is dis 75 solved in 175 cc of absolute xylene and kept at the boiling point with 15 6 g of finelypowdered sodium hydroxide under reflux with stirring during 3 hours using an oil bath temperature of 180 with provision of a water 80 separator Then, without interrupting the heating, 50 g of 2-(N-ethyl-piperidyl-21)-1-chloroethane (B p 99 -103 /13 mm Hg, Beilstein 4 Aufl 20, 105), dissolved in 50 cc of absolute xylene, are added dropwise during 2-, hours, 85 and, without interrupting the stirring, the mixture is heated at the boiling point during a further 2 hours It is then cooled and the reaction mixture extracted with a total of 600 cc of water The xylene solution, dried over 90 potash, is filtered and concentrated as far as possible under partial vacuum at 80 The residue is first freed from excess 2-(N-ethylpiperidy I-21)-1-chloro-ethane at 11 mm Hg. and using an oil bath temperature of about 95 , and is then distilled under high vacuum; The main fraction which passes over under 0.01 mm Hg between 163 and 176 is collected The analytically pure N-llm-chlorophenyll N l 2-(N'-ethyl-piperidyl-2 ')-ethyl 100 1 l-aniline has a boiling point of 166 /0 01 mm Hg. EXAMPLE 3. N lm-bromo-phenyll -N l 2-(Nl-ethylpiperidyl-21 ')-ethyl-1 l -aniline 105 64.5 g of N-(m-bromo-phenyl)-aniline (B p. /0 04 mm, prepared in an analogous manner to the N-(m-chloro-phenyl)-aniline is dissolved in 175 cc of absolute xylene,

15.6 g of finely pulverised sodium hydroxide 110 are added, and the mixture is kept at the boiling point for 3 hours under reflux with stirring using an oil bath temperature of 180 with the provision of a water separator Then, without interrupting the heating 50 g of 2-(N 115 ethyl-piperidyl-21)-l-chloro-ethane (B p 99 103 /13 mm Hg, dissolved in 50 cc of absolute xylene, are added dropwise during 2-, hours and the mixture is heated for a further 2 hours It is then cooled, and the reaction 120 mixture is extracted with a total of 600 cc of water The xylene solution, dried over potash, is filtered and is concentrated as far as possible at 80 C under partial vacuum The residue is first freed from excess 2-(N-ethyl-piperidyl 125 21)-1-chloro-ethane at 11 mm Hg and using an oil bath temperature of about 160 ', and then distilled under high vacuum The main fraction, which passes over under 0 025 mm. Hg between 183 and 188 , is collected 130 784,892 784,892 The analytically pure N lm-bromo-phenyllN l 2-(N'-ethyl-piperidyl-2 ')-ethyl-1 l aniline boils under 0 025 mm Hg at 186 . EXAMPLE 4. N l 2-(N-methyl-piperidyl-2)-ethyl-1 ldiphenylamine. 169 1 g of diphenylamine ( 1 mol) is dissolved in 5 to 6 times its weight of absolute xylene, treated with 46 8 g of sodamide ( 20 % excess) and kept at the boiling point under reflux for an hour Then, without interrupting the heating, 177 6 g of 2-(N-methyl-piperidyl2 ')-l-chloro-ethane of B p 84 /10 mm Hg. ( 10 % excess), dissolved in its own weight of absolute xylene, is added dropwise within 1-1 hours and the mixture is heated at the boiling point for a further 10 hours It is then cooled and the excess sodamide destroyed by the addition of 20 g of ammonium chloride The reaction mixture is extracted several times with a total of the same volume of water The xylene layer is concentrated in vacuum at a bath temperature of 70 , and the residue distilled under high vacuum, the fraction passing over under a pressure of 0 25 mm Hg at 170 -200 being collected. Pure N l 2-(N'-methyl-piperidyl-2 ')-ethyl1 l-diphenylamine boils under O 25 mm Hg at 193 . For preparation of the hydrochloride the base is dissolved in 10 times its weight of absolute ether and treated with etheric hydrogen chloride until the mixture reacts acid towards Congo The precipitated hydrochloride is filtered off and recrystallised from 7 times its weight of acetone The salt melts at 1481500. EXAMPLE 5. N lm-chloro-phenyll -N l 2-(N 1-methylpiperidyl-2 ')-ethyl-1 l-aniline. 203 5 g N-(m-chloro-phenyl)-aniline ( 1 mol) is dissolved in 4 to 5

times its weight of absolute xylene, treated with 46 8 g sodamide ( 20 % excess), and held at the boiling point under reflux for 1 hour Then, without interrupting the heating, 177 6 g of 2-(N-methylpiperidyl-21)-l-chloro-ethane of B p 84 /10 mm Hg ( 10 % excess), dissolved in its own weight of absolute xylene, is added dropwise within 1 hours The mixture is then cooled and the excess sodamide is destroyed by addition of 20 g of ammonium chloride The reaction mixture is extracted several times with a total of the same volume of water The xylene layer is concentrated under vacuum at a bath temperature of 70 and the residue is distilled under high vacuum whereby the fraction passing over under a pressure of 0 08 mm Hg at 160-193 is collected. Pure N lm chloro-phenyll-N-l 2-(N 1methyl-piperidyl-2 ')-ethyl-ll aniline boils under 0 04 mm Hg at 1820. For preparation of the hydrochloride the base is dissolved in 2 times its weight of absolute ethanol and treated with ethanolic hydrogen chloride until the mixture reacts acid towards Congo The residue is concentrated under vacuum at 60 and dissolved in 2-1 times its weight of boiling dioxane On cooling, the hydrochloride crystallises out which, after addition of the same volume of ether as of dioxane used, is filtered off and recrystallised from its own weight of acetone The salt melts at 125127 . EXAMPLE 6 75 N lm-bromo-phenyll -N l 2-(N 1-methylpiperidyl-21)-ethyl-1 l -aniline. 248 g N-(m-bromo-phenyl)-aniline ( 1 mol) is dissolved in 4 to 5 times its weight of absolute xylene, treated with 46 8 g sodamide 80 ( 20 % excess) and held at the boiling point under reflux for 1 hour Then, without interrupting the heating, 177 6 g of 2-(N-methylpiperidyl-2 ')-1-chloro-ethane of B p 84 /10 mm Hg ( 10 % excess), dissolved in its own 85 weight of absolute xylene, is added dropwise within 15 hours The mixture is then cooled and the excess sodamide is destroyed by addition of 20 g of ammonium chloride The reaction mixture is extracted several times with 90 a total of the same volume of water The xylene layer is concentrated under vacuum at a bath temperature of 70 and the residue is distilled under high vacuum, the fraction passing over under a pressure of 0 08 mm Hg at 185 95 201 being collected. The analytically pure N lm-bromo-phenyll N l 2 (NI methyl-piperidy I-21)-ethyl-llaniline boils under 0 06 mm Hg at 193 For preparation of the hydrochloride, the 100 base is dissolved in 12 times its weight of absolute ether and is treated with etheric hydrogen chloride until the mixture reacts acid towards Congo The precipitated hydrochloride is filtered off, dissolved for recrystallisation in 105 its own weight of boiling acetone and treated with half this weight of ether M p 126128

. EXAMPLE 7. l 2-(N'-methyl-piperidyl-2)-ethyl-ll 110 ldi(m-chloro-phenyl)l -amine. 20.0 g di-(m-chloro-phenyl)-amine (B p. 225-230 /25 mm Hg), prepared according to L A Elson and C S Gibson (J Chem Soc. 1931, 301), is dissolved in 90 cc of absolute 115 xylene, treated with 3 95 g of sodamide ( 20 % excess), and held at the boiling point for 1 hour under reflux using an oil bath temperature of 170 Then, without interrupting the heating, 16 3 g of 2-(N-methyl-piperidyl-21)-1 120 chloro-ethane (B p 84 /10 mm Hg) ( 20 % excess), dissolved in 20 cc absolute xylene, is added dropwise within 1 hour and the mixture is heated at the boiling point for 15 hours more It is then cooled and the excess sodamide 125 is destroyed by the addition of 1 0 g of ammonium chloride After addition of 100 cc. of benzene or xylene, the reaction solution is extracted 3 times with 40 cc of water The xylene-benzene layer is concentrated under 130 4 784,892 vacuum using a bath temperature of 70 and the residue is distilled under high vacuum, the fraction passing over under a pressure of 0 01 mm Hg at 175-195 being collected Pure l 2-(N 1-methyl-piperidyl-2 l)-ethyl-1 l ldi(m chloro-phenyl)l-amine boils under 0 01 mm. Hg at 180 . The oily base readily dissolves in mineral acids or in aqueous solutions of organic acids as for example tartaric acid, gluconic acid, oxalic acid, malic acid, and maleic acid. EXAMPLE 8. l 2-(N'-methyl-piperidyl-21)-ethyl-1 l lmchloro-phenyll lm-methoxy-phenyll -amine. 9 1 g (mt-chloro-phenyl) (nm-methoxyphenyl)-amine (B p 142-143 /0 02 mm. Hg.), prepared by suitable modification of the process of L A Elson and C S Gibson (J. Chem Soc 1931, 301) is dissolved in 40 cc. of absolute xylene, treated with 1 83 g of sodamide ( 20 % excess), and kept at the boiling point under reflux for 1 hour using a bath temperature of 170 Then, without interrupting the heating, 7 55 g of 2-(N-methyl-piperidyl21)-1-chloro-ethane of B p 84 /10 mm Hg. ( 20 % excess), dissolved in 7 5 cc of absolute xylene, are added dropwise and the mixture is heated at the boiling point for 15 hours more. It is then cooled and the excess sodamide is destroyed by the addition of 0 5 g of ammonium chloride After addition of 50 cc. of benzene, the reaction mixture is extracted 3 times, each time with

25 cc of water The xylene-benzene layer is concentrated under vacuum using a bath temperature of 70 and the residue is distilled under vacuum, the fraction passing over under a pressure of 0.005 mm Hg at 170-192 being collected. Pure l 2-(N 1-methyl-piperidyl-21)-ethyl-1 llin chloro-phenyll lnm methoxy-phenyllamine boils under 0 007 mmin Hg at 180 . For preparation of the hydrochloride, 10 15 g of the base is dissolved in 150 cc of absolute ether and the solution is made acid to Congo with etheric hydrogen chloride The precipitated hydrochloride is filtered off, dissolved in cc of chloroform, and treated with 75 cc. of benzene, the solution is then poured into 1 to 1 5 litres of petroleum ether (ice-cold), and is then filtered The melting point of the l 2(N 1-methyl-piperidyl-2 l)-ethyl-1 l lm-chlorophenyll lm methoxyphenyll amine hydrochloride is 65-68 (Decomp) after agglomerating above 50 . EXAMPLE 9. N lrm-Methyl-phenyll -N l 2-(N 1-methylpiperidyl-2 ')-ethyl-1 l -aniline. The reaction of 2-(N-methyl-piperidyl-2 ')1-chloro-ethane with N-(m-methyl-phenyl)aniline, by the same process, yields N-lmmethyl-phenyll -N-l 2-(N' methyl-piperidyl21)-ethyl-1 l-aniline, b p 1610/0 007 mm Hg. 1 t EXAMPLE 10. N lm-Methoxy-phenyll -N l 2-(N 1-methylpiperidyl-21)-ethyl-l l -aniline. The reaction of 2-(N-methyl-piperidyl-21)1-chloro-ethane with N-(m-methoxy-phenyl)aniline by the same process, yields N-lmmethoxy-phenyll-N-l 2-(N'-methyl-piperidyl21)-ethyl-1 l-aniline, b p 174 /0 01 mm Hg. EXAMPLE 11. N-l ntm-Chloro-phenyll-N-l 2-(N'-methylpiperidyl-2)-ethyl-1 l -p-anisidine. The reaction of 2-(N-methyl-piperidyl-21)1-chloro-ethane with N-(m-chloro-phenyl)-panisidine by the same process, yields N-lmchloro-phenyll N l 2-(N'-methyl-piperidyl2 ')-ethyl-1 l-p-anisidine, b p 189 /0 005 mm. Hg.

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